Structural dynamics of a thermally silent triiron(II) spin crossover defect grid complex.

The structural evolution of spin crossover (SCO) complexes during their spin transition at equilibrium and out-of-equilibrium conditions needs to be understood to enable their successful utilisation in displays, actuators and memory components. In this study, diffraction techniques were employed to study the structural changes accompanying the temperature increase and the light irradiation of a defect [2 × 2] triiron(II) metallogrid of the form [FeII3LH2(HLH)2](BF4)4·4MeCN (FE3), LH = 3,5-bis{6-(2,2'-bipyridyl)}pyrazole. Although a multi-temperature crystallographic investigation on single crystals evidenced that the compound does not exhibit a thermal spin transition, the structural analysis of the defect grid suggests that the flexibility of the grid, provided by a metal-devoid vertex, leads to interesting characteristics that can be used for intermolecular cooperativity in related thermally responsive systems. Time-resolved photocrystallography results reveal that upon excitation with a ps laser pulse, the defect grid shows the first two steps of the out-of-equilibrium process, namely the photoinduced and elastic steps, occurring at the ps and ns time scales, respectively. Similar to a previously reported [2 × 2] tetrairon(II) metallogrid, FE3 exhibits a local distortion of the entire grid during the photoinduced step and a long-range distortion of the lattice during the elastic step. Although the lifetime of the pure photoinduced high spin (HS) state is longer in the tetranuclear grid than in the defect grid, suggesting that the global nuclearity plays a crucial role for the lifetime of the photoinduced species, the influence of the co-crystalising solvent on the lifetime of the photoinduced HS state remains unknown. This study sheds light on the out-of-equilibrium dynamics of a thermally silent defect triiron SCO metallogrid.

Axial vs equatorial: Capturing the intramolecular charge transfer state geometry in conformational polymorphic crystals of a donor-bridge-acceptor dyad in nanosecond-time-scale.

Two conformational polymorphs of a donor-bridge-acceptor (D-B-A) dyad, p-(CH3)2N-C6H4-(CH2)2-(1-pyrenyl)/PyCHDMA, were studied, where the electron donor (D) moiety p-(CH3)2N-C6H4/DMA is connected through a bridging group (B), -CH2-CH2-, to the electron acceptor (A) moiety pyrene. Though molecular dyads like PyCHDMA have the potential to change solar energy into electrical current through the process of photoinduced intramolecular charge transfer (ICT), the major challenge is the real-time investigation of the photoinduced ICT process in crystals, necessary to design solid-state optoelectronic materials. The time-correlated single photon counting (TCSPC) measurements with the single crystals showed that the ICT state lifetime of the thermodynamic form, PyCHDMA1 (pyrene and DMA: axial), is ∼3 ns, whereas, for the kinetic form, PyCHDMA20 (pyrene and DMA: equatorial), it is ∼7 ns, while photoexcited with 375 nm radiation. The polymorphic crystals were photo-excited and subsequently probed with a pink Laue x-ray beam in time-resolved x-ray diffraction (TRXRD) measurements. The TRXRD results suggest that in the ICT state, due to electron transfer from the tertiary N-atom in DMA moiety to the bridging group and pyrene moiety, a decreased repulsion between the lone-pair and the bond-pair at N-atom induces planarity in the C-N-(CH3)2 moiety, in both polymorphs. The Natural Bond Orbital calculations and partial atomic charge analysis by Hirshfeld partitioning also corroborated the same. Although the interfragment charge transfer (IFCT) analysis using the TDDFT results showed that for the charge transfer excitation in both conformers, the electrons were transferred from the DMA moiety to mostly the pyrene moiety, the bridging group has little role to play in that.

Short- vs. long-range elastic distortion: structural dynamics of a [2 × 2] tetrairon(II) spin crossover grid complex observed by time-resolved X-Ray crystallography.

Spin crossover complexes (SCO) are among the most studied molecular switches due to their potential use in displays, sensors, actuators and memory components. A prerequisite to using these materials is the understanding of the structural changes following the spin transition at out-of-equilibrium conditions. So far, out-of-equilibrium studies in SCO solids have been focused on mononuclear complexes, though a growing number of oligonuclear SCO complexes showing cooperative effects are being reported. Here, we use time-resolved pink Laue crystallography to study the out-of-equilibrium dynamics of a [2 × 2] tetranuclear metallogrid of the form [FeII4LMe4](BF4)4·2MeCN ([LMe]- = 4-methyl-3,5-bis{6-(2,2'-bipyridyl)}pyrazolate). The out-of-equilibrium spin state switching induced by a ps laser pulse demonstrates that the metallogrid exhibits a multi-step response similar to that reported for mononuclear complexes. Contrary to the mononuclear complexes, the metallogrid shows two types of elastic distortions at different time scales. The first is a short-range distortion that propagates over the entire Fe4 grid complex during the ps time scale, and it is caused by the rearrangement of the coordination sphere of the photo-switching ion and the constant feedback between strongly linked metal ions. The second is a long-range distortion caused by the anisotropic expansion of the lattice during the ns time scale, observed in mononuclear materials. The structural analysis demonstrates that the long-range prevails over the short-range distortion, inducing the largest deformation of both the entire grid and the coordination sphere of each metal ion. The present study sheds light on the out-of -equilibrium dynamics of a non-cooperative oligonuclear complex.

Metal-to-metal communication during the spin state transition of a [2 × 2] Fe(II) metallogrid at equilibrium and out-of-equilibrium conditions.

Spin crossover (SCO) complexes are prototypes of materials with bi- or multi-stability in the solid state. The structural evolution during their spin transition is a key feature to establish the foundations of how to utilize this type of material. So far, ultrafast time-resolved structural investigations of SCO solids have been focused on monometallic complexes, though an increasing number of oligometallic SCO complexes showing cooperativity effects are being reported. Here, we used single crystal X-ray crystallography and time-resolved pink Laue photocrystallography to study the molecular reorganisation during the thermal and photoinduced SCO of a [2 × 2] tetranuclear metallogrid of the form [FeII4LMe4](BF4)4·2MeCN ([LMe]- = 4-methyl-3,5-bis{6-(2,2'-bipyridyl)}pyrazolate). A multitemperature crystallographic investigation on single crystals reveals an effective communication between the metal centres during thermal SCO, observed by the simultaneous transformation of the coordination polyhedra of both crystallographic-symmetry independent metal atoms accompanying the SCO in only one of them. Time-resolved photocrystallography results reveal the different molecular responses between mononuclear and oligonuclear complexes, after light irradiation with a picosecond laser pulse. While mononuclear SCO complexes reorganise once during the first nanosecond after excitation, the tetranuclear metallogrid exhibits a multiple structural rearrangement in the same span of time. Such behaviour is attributed to the elastic communication between metal atoms, which allows the propagation of a short-range elastic distortion over the entire Fe4 grid complex. The present study sheds light on the importance of strong elastic coupling of metal atoms during the correlated spin transition of oligometallic complexes.

Ultrafast sorting: Excimeric π-π stacking distinguishes pyrene-N-methylacetamide isomers on the ultrafast time scale.

Pyrene based molecules are inclined to form excimers through self-association upon photoexcitation. In this work, the pyrene core is functionalized with the N-methylacetamide group at the position 1 or 2 to develop pyren-1-methylacetamide (PyMA1) and pyren-2-methylacetamide (PyMA2), respectively. Upon photoexcitation with 345 nm, a portion of molecules in PyMA1 and PyMA2 solutions at ≥1.0 mM have formed static excimers. The steady state spectroscopic measurements suggest that, whether it is the dimerization of molecules in the ground state (GS) or in excimer formation, characteristic signs are more pronounced in PyMA1 than its isomeric counterpart, PyMA2. The shift of the excimer band in their respective emission spectra suggests that the extent of overlap in π-π stacking is greater for PyMA1 than for PyMA2 in the excited state. The optimized geometry of dimers in toluene shows that the overlapping area between the pyrene moieties in π-π stacking between the dimers is greater for PyMA1 than for PyMA2 in GS. The natural bond orbital analysis with the optimized GS geometries shows that the stabilization/interaction energy between the dimers in π-π stacking is higher in PyMA1 compared to PyMA2 in toluene. The transient absorption (TA) measurements in toluene over the fs-ps regime (fs-TA) showed that the formation of static excimers with pre-associated dimers in PyMA1 happens in ∼700 fs whereas the excimers for the pre-associated dimers in PyMA2 have formed in slightly slower time scale (∼1.95 ps). Contrary to what was observed in solution, the extent of overlap in π-π stacking is lower for PyMA1 dimers (∼17%) than for PyMA2 dimers (∼37%) in single crystals.